Glycine imides in turbine oil



r 3,003,961 GLYCINE IMIDES IN TURBINE 01L I Harry J. Andress, Jr., Pitman, and Paul Y. C. Gee,

'Woodbury, N.J., assignors to Socony Mobil Oil Company, Inc a corporation of New York a a No Drawing. Filed June 10, 1959, Ser. No. 819,234

a V 4 Claims. (Cl. 252-33.6)

This invention relates to antirust compositions. It

2 amounts and with the elimination of Water of condensa-. tion. In the case of the anhydride, there will be formed one mole of water per mole of reactant, and with the acid, two moles of water are formed. Accordingly, the

5 condensation will be carried out at temperatures 'of between about 150 C. and about 250 0., preferably between about 175? .C- n about 200 C. The time of reaction will b'e'dependent; of course, upon the reaction temperature employed. Reaction Will'continue until the is more particularly concerned with mineral lubricating 10 required amount of water of condensation has evolved.

oils containing certain succinimides and salts thereof.

As is well known to those skilled in the art, the rusting of ferrous metal surfaces has been a common occurrence in the field of lubrication. This has been a serious Generally, the time will vary between about 2 hours and about 6 hours. Shorter reaction times are required if water is removed by'azeotropic distillation." Suitable liquids which form azeotropes with water are'non-polar problem in steam turbine lubrication, particularly during solvents, such as benzene, toluene, xylenes, etc.

the initial operation of new installations. Rusting is most pronounced at points where the clearance between bearmg surfaces is very small, as in the governor mechanism. l'his is usually caused by water entering the oil supply,

The-alkenyl succinic acid anhydride reactant can have between about 8 and about 35 carbon atoms in the alkenyl radical, and preferably between about 10 and about '14 carbon atoms. Non-limiting examples of the alkenyl sucas by condensation, and becoming entrained in the oil cinic acid anhydride reactants are octenyl succinic acid throughout the circulating system, thereby coming into contact with the ferrous metal surfaces. Manifestly, this constitutes a menace to the operational life of the turbine;

Many materials have been proposed as addition agents anhydride, diisobutenyl succinic acid anhydride, Z-metIiyI? heptenyl succinic acid anhydride, 4-ethylhexenyl succinic acid anhydride, nonenyl succinic acid anhydride, decehyl succinic acid anhydride, undecenyl' succinic acidanh'y= to impart antirust properties to lubricating oils. Particudride, dodecenyl succinic acid anhydride, triisobutenyl larly, in the case of rust protection in the presence of sea water, as in marine turbine lubrication,-mest ceni hyride,:tetradecenylsuecinic aci-d anhydride,:hesadesen pounds used have been materials containing two or more carboxyhc acid groups (-COOH); Monocarboxylic succinic acid anhydride, tetrapropenyl succinic acid an yl succinic acid anhydride, ll-tricosenyl succinicjanhy dride, and 17-pentatriaconteny1 succinic anhydride. As

acids have generally not been efiective in marine service. mentioned hereinbefore, the alkenyl succinic acids corre- It has now been found that antirust properties in the presence of sea water can be imparted to lubricating oil by the addition of certain cyclic imides. it has been discovered that certain alkenyl succinimides and amine sponding to these alkenyl succinic acid anhydrides can be used to prepare the compounds of this invention. The amine salts of the N-carboxymethyLalkenyl-suc cinimides are prepared readily by warming the succi;

salts thereof are effective antirust additives for turbine nimide with an equimolar amount of tertiary-alkyl primary oils.

Accordingly, it is a broad object of this invention to provide novel rust inhibitors. Another object is to provide lubricating oils that are inhibited against rusting of amine. The addition takes place readily, without the elimination of water, but it is facilitated by heating to temperatures of between about 50 C. and about 100 C.

The amines utilizable in forming the salts of the. N-

ferrous metal surfaces in the presence of sea water. A carboxymethyl-alkenyl-succinimides are the tertiary-alkyl,

further object is to provide an antirust turbine oil containing succinimide rust inhibitors. A specific object is to provide a turbine oil containing certain alkenyl succinin'ides and salts thereof. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.

In general, the present invention provides a mineral lubricating oil containing a small amount, sufficient to prevent rusting of ferrous metal surfaces, of (1) an N- primary, monoamines in which a primary amino (NH group is attached to a tertiary carbon atom and which contain between about 6 carbon atoms and about 30 carbon atoms in the tertiary-alkyl radical; and mixtures thereof. These amines all contain the terminal group,

carboxymethyl'alkenyl vsuccinimide containing between Non-limiting examples of the amine reactants are t-hexyl about 8 carbon atoms and about 35 carbon atoms in the alkenyl group or (2) the salts of l) with tertiary-alkyl,

primary amines having a tertiary carbon atom attached to the nitrogen atom and containing between about 6 primary amine, t-octyl primary amine, t-nonyl primary amine, seem pninaary aa ine ededecyl primary carbon atoms and about 30 carbon atoms per tertiarycosyl primary amine, and bmacontyl Primary i alkyl radical.

The novel addition agents utilizable in this invention are N-carboxymethyl-alkenyl-succinimides and amine salts "thereof with tertiary-alkyl primary amines. The

The amine reactants can be prepared in several ways well known to those skilled in the art. Specific methods of preparing the t-alkyl primary amines are disclosed in the Journal of OrganicChemistry, vol. 20, page 295 succ contemplated herein can be P p by et seq. (1955). Mixtures of such amines can be made several methods known to the art for making cyclic insides. Most feasibly, they are prepared by reacting an alkenyl succinic acid anhydride or an alkenyl succinic acid with glycine (aminoacetic acid) in equimolar from a polyolefin fraction (e.g., polypropylene and polybutylene cuts) by first hydrating with sulfuric acidand water to the corresponding alcohol, converting the alco-' hol to alkyl chloride with dry hydrogen chloride, and:

Patented-Oct. 10, 1961 finally condensing the chloride with ammonia, under pressure, to produce a t-alkyl primary amine mixture.

'The N-carboxymethyl-alkenyl-succinimides and the amine salts have the structures, respectively:

ecerea nueta' percent and about 10 percent, 'by weight, are used.

Oft hersubstances canbeadded to the lubricating oil to impart other properties thereto. F9 1" enample, there may be added antioxidants, pour point de pne's'sants, V. I.

imp ve and E- e .Ih following p i sx m e ar $9 t v q fjllustrating the antirnst lubricants got this invention and pf demonstrating the effectiveness thereof. It is to beunderstood that this invention is not to be limited to the particular reactants employed, or to the operations and manipulations described therein. Other reactants, as described hereinbefore, can be employed, as those skilled in the art will readily understand.

AMIC ACIDS AND SALTS The salt forming amine reactant used in the specifi c working examples is a mixture of purean ines. 'fAmine A is a mixture of primary amines having a carbon atom ofa tertiary butyl group attached to the'amino NH2) r up an containing. 121 1. .sat lq qtu ps amine molecule and averaging 12 carbon atoms per molecule. This mixture contains, by weight, about 85 percent tertiary dodecyl amine, about percent tertiary pentadecyl amine, and relatively small amounts, i.e., less than about 5 percent of amines having less than 12 or more than 15 carbon atoms.

Example] ,A mixture of 37.5 grams (0.5 mole) glycine and 150 grams (0.5 mole) tetrapropenyl succinic' anhydride were slowly heated to a temperature of .about 200 C. over a period of about 12 hours. Nine grams (0.5 mole) of water were evolved during the coursepf the -reaction.

Example 2 A mixture of 37.5 grams (0.5 mole) glyeine and 150 grams (0.5 mole) tetrapropenyl succinic anhydride were slowly heated to a temperature of aboutZOO C. over a period. of about 12 hours. The mixture was cooled toabout 75 C. and 100 grams (0.5 mole) of amine A was added. 'The mixturewas stirred-forabout 2 hours at 100 C. to insure complete reaction.

Example 3 Two mineral oil blends were prepared. Each blend contained a small amount of one of the additives described in Examples 1 and 2. Two base oils were used. Oil X is a highly solvent-refined mineral lubricating oil having 31 API gravity and a Saybolt Universal Viscosity of 150 seconds at F. Oil Y is a highly solvent refined Mid-Continent oil having 29 API gravity and a Saybolt Universal Viscosity of 415 seconds at 100 F. Both are typical steam turbine lubricating oils. These blends were subjected to the ASTM Rust Test D665-44T using synthetic sea water. The composition of each blend and test result are setforth in Table I.

The test method used .to distinguish the rusting characteristics of lubricating oil blends was the ASTM test D665 -44T for determining Rust'Prev enting Characteristics of Steam Turbine Oils in Presence of Water, in which synthetic 'sea water was used. The synthetic sea water contained .25 grams of sodium chloride, 11 grams ofmagnesium chloride hexahydrate, 4 grams or sodium suliate, and"1.2 grams of calcium chloride perliter. this test a cylindrical polished steel specimen issuspended and soaked in 300 cubic centimeters of the oil under test at F. for thirty minutes. Thirty cubic centimeters of synthetic sea waterY are added .and the mixture is stirred at 1000 rpm. After 48 hours, the steel specimen islremovedand examined for 'evidence of rust on the portion of the specimen which hangs in the oil. ln order to pass thistest, the test specimen must be entirely free of rust. X

Conc'n, .AS'IM Addlttv e of Egarnple; Wt. Base Rust Percent Oil Test Result none X Fail.

0. 10 X Pass. 0.05 Y liass.

-=It wi1l beapparent to thoseskilled in the art that. the alkenyl succinimides andamine salts thereof are efiective to impart antirust properties to lubricating oils, in .the presence of seat water. Thus, the mineral oil compositions are highly eifective for severeservice, such as,.in marine turbine lubrication.

Although the present invention has been.described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the "art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims. K i i What is claimed is: l I V I 1. A mineral lubricatingoil containing a small amount, suflicient to prevent rusting of ferrous metal surfaces, ,of at least one compound selected fromthe group consisting of- (1) an N-carboxymethyl-alkenyl-succinimide containing between about 8 carbon atoms and about 35 carbon atoms in the alkenyl group and (2) amine salts of (l) with tertiary-alkyl primary amines having a tertiary carbon atom attached to the nitrogen atom andcontaining between about 6 carbon atoms and about 30 carbon atoms per tertiary-alkyl radical.

2. The lubricating oil composition defined in claim 1, wherein said mineral lubricating oil is a steam turbine lubricating oil and wherein said compound is present in amounts varying between about 0.001 percent and about 10 percent, by Weight of the oil.

3. A steam turbine lubricating oil containing between radical and having an average of about 12 carbon atoms per molecule.

References Cited in the file of this patent 5 UNITED STATES PATENTS 2,604,451 Rocchini July 22, 1952 2,790,779 Spivack et a1. Apr. 30, 1957 

1. A MINERAL LUBRICATING OIL CONTAINING A SMALL AMOUNT, SUFFICIENT TO PREVENT RUSTING OF FERROUS METAL SURFACES, OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) AN N-CARBOXYMETHYL-ALKENYL-SUCCINIMIDE CONTAINING BETWEEN ABOUT 8 CARBON ATOMS AND ABOUT 35 CARBON ATOMS IN THE ALKYL PRIMARY AMINES HAVING A TERTIARY (1) WITH TERTIARY-ALKYL PRIMRY AMINES HAVING A TERTIARY CARBON ATOM ATTACHED TO THE NITROGEN ATOM AND CONTAINING BETWEEN ABOUT 6 CARBON ATOMS AND ABOUT 30 CARBON ATOMS PER TERTIARY-ALKYL RADICAL. 